dorsal/arxiv
View SchemaPath integral formulation for quantum nonadiabatic dynamics and the mixed quantum-classical limit
| Authors | Vinod Krishna |
|---|---|
| Categories | |
| ArXiv ID | physics/0702220 |
| URL | https://arxiv.org/abs/physics/0702220 |
| DOI | 10.1063/1.2716387 |
| Journal | J. Chem. Phys. 126, 134107 (2007) |
Abstract
This work identifies geometric effects on dynamics due to nonadiabatic couplings in Born Oppenheimer systems and provides a systematic method for deriving corrections to mixed quantum-classical methods. Specifically, an exact path integral formulation of the quantum nonadiabatic dynamics of Born Oppenheimer systems is described. Stationary phase approximations to the propagator for full quantum dynamics are derived. It is shown that quantum corrections to mixed quantum classical methods can be obtained through stationary phase approximations to the full quantum dynamics. A rigorous description of the quantum corrections due to electronic nonadiabatic coupling on the nuclear dynamics within the Ehrenfest framework is obtained. The fewest switches surface hopping method is shown to be obtained as a quasiclassical approximation to the dynamics and natural semiclassical extensions to include classically forbidden nonadiabatic transitions are suggested.
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"abstract": "This work identifies geometric effects on dynamics due to nonadiabatic\ncouplings in Born Oppenheimer systems and provides a systematic method for\nderiving corrections to mixed quantum-classical methods. Specifically, an exact\npath integral formulation of the quantum nonadiabatic dynamics of Born\nOppenheimer systems is described. Stationary phase approximations to the\npropagator for full quantum dynamics are derived. It is shown that quantum\ncorrections to mixed quantum classical methods can be obtained through\nstationary phase approximations to the full quantum dynamics. A rigorous\ndescription of the quantum corrections due to electronic nonadiabatic coupling\non the nuclear dynamics within the Ehrenfest framework is obtained. The fewest\nswitches surface hopping method is shown to be obtained as a quasiclassical\napproximation to the dynamics and natural semiclassical extensions to include\nclassically forbidden nonadiabatic transitions are suggested.",
"arxiv_id": "physics/0702220",
"authors": [
"Vinod Krishna"
],
"categories": [
"physics.chem-ph",
"cond-mat.mtrl-sci",
"quant-ph"
],
"doi": "10.1063/1.2716387",
"journal_ref": "J. Chem. Phys. 126, 134107 (2007)",
"title": "Path integral formulation for quantum nonadiabatic dynamics and the mixed quantum-classical limit",
"url": "https://arxiv.org/abs/physics/0702220"
},
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